OK give this a spin!
Put a PSX CD in your Regular Drive
Click Start then Run
type in "Command" (without the quotes)
In the DOS Box, type.
C:
then..
CD \Windows\Desktop\ePSXe
now type...
ePSXe -cdrom F: -nogui
Now what you should get is both the Sony Screen and then the PlayStation Screen.
If it hangs at the Sony screen, then this usually means (to me) that the CDR Plugin cant read the CD properly, try the Barrart-Kazzuya one or Pete's!
If it hangs at the PlayStation Screen, then CDRom options might need tweaking, like Accurate CDR Timing!
If Game works... Smile!
If not, press Escape and copy what has outputted into that DOS window and paste it here!